Azo dyestuffs



Patented Aug. 27, 1929.

UNITED STATES PATENT OFFICE.

FRITZHESS, OF HOFHEIM-ON-THE-TAUNUS, GERMANY, ASSIGNOR TO GENERAL ANI-LINE WORKS, INC., OF NEW YORK PT. Y., A CORPORATION OF DELAWARE.

Azo mms'rorrs.

No Drawing. Application filed. March 30, 1928, Serial No. 266,101, andin Germany April 4, 1927.

,My present invention relates to azo dye stufi's, more particularly todyestuffs of the following general formula:

wherein X stands for hydrogen or alkyl, Y for any acid residue, Z forany monovalent substituent particularly for one of the groupsalkyl,aralkyl,aryl, oxyalkyl, NH-aryl,

alkyl R1 for NR1, NH-alkyl or N are obtained dyestufl's, which dye silkand cotton mordanted with tannic acid valuable shades. By using forinstance tolusafr'anine as diazo component, beautiful claret-red tintsare produced such as have hitherto not been obtained with any of theknown safranine-azo-dyestufis.

' When using a safranine of the type of the dialkyl-safranines,violet-black to greenishblack dyestufis are obtained which are likewisecapable of dyeing silk and cotton mordanted with tannic acid.

Owing to the shades they yield and their solubility, a number of saltsof these dyestuffs are distinguished by their excellent copying powerand are, therefore, particular ly suitable for the manufacture ofcopying materials, such as for instance copying pencils, copying inks,copying printing-pastes,

typewriter-ribboiasiand the like;

The following apples illustrate my .in-

vention, but they are not intended to limit it; i

the parts are by weight 1. 10.5 partsof tolusafranine are dissolved in1400 parts of water and this solution is diazotized at about 10 with 15parts of hydrochloric acid (equivalent 120) and 2 parts of nitrite of100 per cent strength.

After acidifying the diazo solution by means of 12 parts of anhydroussodium acetate, a solution of 4 parts of acetylacetone in 10 parts ofalcohol is added thereto. The coupling is complete after one hour andthe mass is saltedv with 8 to 10 per cent of sodium chloride. Theclaret-red dyestuff which. is thus obtained with a yield of 10 parts, isfiltered'and dried at C. It has the following formula anhydrous sodiumacetate and mixed with a solution of 6 parts of acetoacetic anilide in15 parts of alcohol.

The coupling is complete af er several hours. The greenish-blackdyestuif thus obtained is precipitated by means of 15 per cent of sodiumchloride, if required while adding a small quantity of zinc chloride,then filtered and'dried at 50 0. Its yield amounts to 21 parts and ithasthe following formula 2 the manufacture of copying materials, theyfollowing formula:

must be isolated in another manner: may be done for instance as follows:

When the coupling is finished, the solution is rendered alkaline by theaddition of sodium carbonate, whereby the base of the dyestuif isprecipitated and can'be filtered. The paste is then acidified, forinstance by the addition of an acetate,'and dried at 50 C.

I claim:

1. As new products, the dyestuffs of the following general formula:

This

wherein X stands for hydrogen or alkyl, Y for any acid residue, Z forany monovalent substituent,

. yang! R1 for NH], NH-alkyl or N i \alkyl and R for hydrogen or alkyl,being brownish-red to black powders, soluble in water to bluish-red orblackish-violet to greenishblfifk solutions and dyeing well. cotton ands1 T i 2. As new products the dyestuffs of the wherein X stands forhydrogen or alkyl, Y

for any acid residue, Z for alkyl, aralkyl, aryl, oxyalkyl, NH-aryl,

R1 for NHz, NH-alkyl or N \alkyl and R for hydrogen or alkyl, beingbrownish-red to black powders, soluble in water to bluish-red orblackish-violet to greenishblack solutions and dyeing well cotton andsilk.

3. As new products, the dyestufis of the following formula:

wherein X stands for hydrogen or alkyl, Y for a halogen atom, Z foralkyl, aralkyl, aryl, oxyalkyl, NH-aryl,

. fflky,

Rx for NR1, NH-alky] otN \alkyl and R for hydrogen or alkyl, beingbrownish-red to black powders, soluble in water to bluish-red orblackish-violet to greenishbllzipk solutions and dyeing well cotton ands1 a 4. As new products, the dyestuffs of the following formula:

wherein X stands for hydrogen or alkyl and Z for alkyl or NH-aryl, beingbrownish-red to black powders, soluble in water to bluishred orblackish-violet to greenish-black solutions and dyeing well cotton andsilk..

5. As new products, the dyestuffs of the following formula: I

wherein X stands for hydrogen or alkyl and Z for alkyl or NH-aryl, beingbrownish-red powders, soluble in water to bluislbred solu- 7. As a newproduct, the dyestufls of the tions and dyeing well cotton and silk.following formula: 6 6. As new products the dyestufl's of the H0 Nfollowing formula: a 5 20 Han NU (EH1 Hm \\N \N=N(IJH C=O Hm N Cl N-N(IJH I a c=o 10 o a'lkyl 25 being a, brownish-red powder, soluble inwater to a bluish-red solution and dyeing well being brownish-redpowders, soluble in water cotton and silk. k to bluish-red solutions anddyeing well oot- In testimony whereof, I afiix my signature. 15 ton andsilk. FRITZ HESS.

